Dyeing panama hats



Patented June 29, 1943 UNITED STATES PATENT OFFICE DYEING PANAMA HATS George M. Rickus, William L. Braun, and Stanley G. Hofiman, Norwalk, Conn., assignors to I Hat Corporation of America, Norwalk, Conn,

a corporation of Delaware No Drawing. Application May 4, 1940,

1 Serial No. 333,424

7 Claims.

This invention relates to palm fibers, and to the process of dyeing palm fibers. An important application of the present invention .is in the Panama hat industry.

It has been customary to manufacture Panama hat bodiesin foreign countries. Bruises ordinarily develop during the weaving of the hat bodies from the palm fiber. Partly to make the bruised spots less noticeable, it has been customary to pound the fibers and to rub sulfur into them. The hats have ordinarily been shipped in a folded condition, and bruises have developed during shipment. Hats are conventionally bleached at bleacheries, and shipped to hat factories for finishing operation.

Several methods of dyeing Panama hats have been tried in the past. None of the processes have been satisfactory. Dyed Panama hats have been objectionable because:

(1) There has been little penetration of the dye. The. dyeing process has been almost a surfacecoating. Whenever a fiber has been abraded or broken, as for example in handling, the crosssection has shown the ring of surface dyeing and a center of-undyed palm.

(2) There, has been too little flexibility, and

too much brittleness. :Dyed Panama fibers have been both weak and fragile. (3) There has been a lackof uniformity of color distribution, because the dyeing processes have affected bruised and unbruised portions diffe'rently, and because the dyestuffs inherently produced some shading. i

Accordingly, it is an important object of the present invention to provide as a new product a dyed Panama hat having little brittleness and the general physical characteristics ofan undyed hat.

Another object is to provide a process by means of which the dye is made to penetrate throughout the fiber, so that if the hat becomes bruised or cut, the cross-section of the fiber will show ap- A feature resulting in the attainment, of the foregoing objects is the use of a dyeing solution containing dyestuffs chosen from each of two classes of dyestuffs.

Another feature is the control oithe temperature of the dyeing solution to effects. more thorough distribution and uniform penetration of the color. I

Other features include:

The use of a wetting out process to make the palm fibers more susceptible to the penetration of the color.

The use of an emulsifying agent to stabilize a suspension of a water insoluble dye.

The use of a lacquer on the Panama hats to ,control the reflection of light from the hat.

The use of a. process of preparing, shipping, and bleaching unfinished Panama hat bodies without extensively bruising the same.

Other objects and features can be appreciated upon reading the detailed description and claims hereinafter.

The detailed description which follows is under various headings to facilitate an understanding or the process and the article of manufacture. The present invention is not limited to the details described herein, for the invention is capable of other methods of operation.

Therefore, the pnra'seology used is for the purpose of description and not or limitation.

'Pnrrluzmd Umgmisarn HAT Booms .According to thepresent invention Panama hat bodies; woven with the minimum amount or proximately the same uniform color throughout.

A further object is to provide a method of dyeing palm fibers which will give a substantially uniform color to both the bruised and unbruised portions of the fiber.

Another object is to provide a manufacturing process minimizing the brulsingof theflbers of a Panama hat.

Yet another object is to provide a process giving uniform distribution of color upon a Panama hat or like article.

A still further object is to provide a dyeing process adapted to dye unbleached and semibleached, as well as bleached Panama hats.

Another object is to provide a process by means of which the reflection of light from a dyed Panama hat is more accurately controlled.

Another object is to provide a process for making waterproofed fibers;

bruising; are shipped as untrimmed bodies. Ormnarily hat bodies are pounded, and treated with sulrur, but according to the process or thepresent invention, the Panama hat bodiesare given as little bruising as possible, and no sulfur is rubbed or pounded into the fibers at any time.

Preferably the untrlmmed hats are shipped *with the crown ofeach hat. inside the crown of the hat above it. Because they are untrimmed hats, there is little possibility of bruising either the brim or the crown;

Before being bleached the untrimmed sulfurfree hat bodies are givena preliminary, blocking. An ordinary bleaching solution hasbeen round satisfactory. Better results are obtained with outlined above is followed the amount of'bruising is minimized.

Warrmc Our The preferably untrimmed, sulfur free, blocked, and bleached Panama hat bodies are then placed in water to effect a thorough wetting of the fibers. Panama hat workers can readily determine whether the fibers are thoroughly wetted by the feel of the material. If the fibers are immersed for an unduly prolonged time, they are so soft as to be very easily bruised, and if they are not thoroughly wetted, the penetration of the dye is not as complete and/or as rapid as desired. The exact period of time necessarily varies according to the prior treatment of the hat, the diameter of the fiber, and many other variables, but can be easily determined for each batch by a person skilled in the art. Whether semibleached hat bodies, unbleached hat bodies, raw palm fiber, or equivalent materials are to be dyed, they are subjected to a thorough wetting out process, suflicient to penetratingly soak the material, but insuflicient to make the material exceptionally susceptible to bruising.

Soaking the hats in water for twelve hours at a temperature of 50 to 70 F. has been found to be satisfactory, as has soaking in a water solution containing one-tenth of one per cent of Nekal NS (sodium sulfonate of a fatty acid ester),

at 100'F., for five hours. Instead of using Nekal NS, Peregal O (ethylene oxide condensate with higher fatty alcohol), Naconal NR (sodium alkylarylsulfonate),. Gardinol (sodium sulfate of technical oleyl. alcohol), Clarol, Decersol OT (sodium salt of dioctylsulfosuccinate) Sulframine DRX, or an equivalent wetting agent may be used.

PREPARATION or DYE LIQUOR According to the present invention, a dyeing solution is used which contains at least one of each 01' two classes of dyestuifs. It has been found that certain kinds of dyestuffs will dye the bruised fibers, and that certain other kinds of dyestuffs will dye the unbruised fibers. It has also been found that a dye bath containing at least one of each class of dyestuff will satisfac'-.

torily dye a somewhat brulsedPanama hat. It is possible to produce a hat having the same shade upon both the bruised and the unbruised portions, or having shades so nearly the same that the difference cannot be normally detected. However, the bruised and unbruised portions reflect light differently, and the, bruised spots in the dyed but unfinished hat can sometimes be detected by means of the differences in reflection of light. To obtain most satisfactory results, therefore, it is desirable that the hats, prior to the dyeing operation, be treated and handled in a manner to minimize bruising. 1

The class of dyestuffs satisfactorily dyeing the unbruised portion of the fibers hereinafter sometimes designated as "class A dyestuffs" has been found to include two kinds, namely: acetate dyestuffs; and spirit or oil soluble dyestufis. Acetate dyestuffs are insoluble in but dispersible in water, and were originally developed for dyeing acetate rayon. Acetate dyestuffs are known by that name in the trade. Similarly spirit or oil soluble dyestuffs include those which are soluble in either oil or spirit, and are known to the trade by that name. In referring to oil or spirit solu- Grams Celliton Yellow GA 4.455 Ciba Orange 3R 1.485 Celliton Blue Green B .128

Total class A dyestuffs 6.068

Fastusol Yellow 2G 3.465 Brill Pure Yellow 6 GS; 2.970 Benzo Rhodmmp ,297

Total class B dyestuffs 6.732

Total dyestuffs 12.800

ble dyestufis those appreciably soluble in any of eral oil, ethyl alcohol, glycol, butyl acetate, Cellosolve, Carbitol, etc. are meant to be included.

Among the class A dyestuffs that have been found satisfactory are Celliton Fast Yellow GA, Cibacet Red B, Celliton Fast Blue FR, Celliton Fast Pink RF, Celliton Fast Orange R, Ciba Orange 3R, Celliton Fast Blue Green B, Celliton Fast Blue FFC, Azosol Fast Red BB, and Azosol Fast Red 3B.

The class of dyestuffs atisfactorily dyeing the bruised portion of the fibers, hereinafter sometimes designated as class B dyestuffs ha been found to include two kinds, namely: direct dyestuffs; and neutral dyeing acid dyestuffs.

Among the class B dyestuff that have been found satisfactory are Brilliant Indocyanine G, Brilliant W001 Blue FEB Ex (Prototype 40), Fastusol Yellow 2G (Rowes C. I. 346), Brilliant Pure Yellow 6 GS Conc. (Rowes C. I. 802), Benzo Rhoduline Red B (Schultze C. I. 305), Benzo Orange R Conc. New, Diamini Brown 3 GTA, Azo Fast Yellow CGG, Azosol Fast Violet BB, Fastusol Red 4 BA, Fastusol Red L5B, Azosol Fast E511; LRA, Fastusol Pink G, and Fastusol Red All of said class A and class B dyestuffs can be purchased through General Dyestuffs Corporation, New York city.

At least one class A dyestuff is mixed with GardinoL or an equivalent emulsifying agent, and then dispersed in boiling water. To this suspension is added at least one class B dyestuff, and enough water is added to dissolve the class B dyestufi. Those skilled in the art are accustomed to preparing pastes of this nature by similar procedures. The ratio of class A to class B dyestuff is dependent partly upon the relative proportion of bruised to unbruised fibers to be dyed, but even more dependent upon the depth of shade desired. The degree of matching oi shades also effects the AzB ratio.

If eighteen Panama hats weighing approximately 990 gms. are to be dyed a canary yellow, a dyeing paste may be made up as follows:

If thirteen hats weighting approximately 685 gms. are to be dyed a roseleaf pink, a dyeing liquor may be made up as follows:

. In preparing a dye the Similarly other shades are produecdby preparing dye paste containing at least one dyestuff from each of the two classes.-

Water. and dye paste are mixed to prepare a dy bath of. suitable dyeing level, ascanbereadily determined by those skilled in the art. Ordinarily about 80 parts of water to 1 part by. weight of Panama hats hasbeen found satisfactory.

An emulsifying agent is also .addedtothe; dye h bath. The exactamount depends upon the na- .ture of the emulsifying agent, but is ordinarily.

about 5% of the weight of-ihepa-lm :fiber'being have" been found to be excellent emulsifying chemicals.

bath for dyeing palm fiber ry yellow, the followingpronortions may be a "In preparing 3 eye bathfordyeing pajlm fiber roseleaffpink, the following proportions may be mr'r. "men the palm fiber is introduced. f The temperature of the dyeingsolution isgradually raised toor near to the boiling point, normally" within about twenty-five minutes bug m in not less than twenty nor more than'thirty minutes. The dyeing solutionis then-maintained at the high temperature, most conveniently at i the boiling point; which is normally eboutziz ll, until the desired penetration of the-- dye is achieved. Keeping the dyeing solution at the boilingpoint for an hour'hasbeen foundto'give .tisfactory penetration, but the] period necessarily varies with the condition of the palm fiber, the shade being dyed; and other factors. 0

i The dyeing solution is then drained from the inn, and the hats are allowed todryL; Although anysuitable drying means is effective, it has been found that'permitting the hats to dry under nortotbejpresent invention the reflection characteristics of any Panama hat may be improved by the application of a uniform reflection lacquer. According to. the present invention, incorporating synthetic resins having suitable reflective and refractive properties, ina lacquer produces a uniform reflection lacquer. A lacquer which has been found satisfactory for imparting uniform reflection to adyed palm fiber is:

m the above formula .P a 5' refe s to Pierce and Stevens, of Buffalo, New York. While the exact formulas of'the three Pierce fand'Stevens compositions are not obtainable, it

is believed that similar compositions would have the following formulas: i

I Hot thinner P a s #407 i Parts 7 Isopropy} almhnl Normal butyl alcohol 1 Hydrogenated naphtha v6 o u c f f 6 Ethylene glycolmonoethyl ether Q 6 Hatsizingllwq rlks #8068 M I f 1. i 1 Parts 5 second nitrocellulose 10 Celluloseethyl ether 10 Tribeta monochlorethyl phosphate 2 Bretylether condensate of dimetbylol urea -2 Ethyleneglycol monoethyl ether 61 Toluene L63 Hydrogenated naph 61 "Normal butyl alcohol' 10 .I P 0lI7lalcohol 15 q Lacquer thinness #35269 .Isopr'opyl alcohol 2 Normal butyl alcohol 1 Hydrogenated naphtha 6 Toluene. if 6 f Ethylene glycol monoethyl ether 5 mal room conditions is quite satisfactory and the most economical method of drying.

i i 'Lncaunamc spots, the light reflects from therespective portions vdifferently. It has been found that by the use of suitable lacquersit is possible to develop a uniform reflection or light from the entire hat. Inthe past uniform reflection of light from the.

bruised and unbruis'ed portionshas been achieved partly by means of the sulfur treat tion may be taken care by means of a lacquer developed by the present invention. According 75 dyed material having substantially the physical V dried and dyed hats have the "aameshade upon the bruised and unbruised It will be understood that' Du Pont the. acrylate resin #2984 is monomethylmethacrylate;

when the latter is resorted to, the hat ispreferablygiven a preliminary coating of the lacquer bydipping in a lacquer such, as given above.

"Then the hat is dummy blocked, anddipped in f thelacquer again. The flnal pressingfollows the .secondqdipping. Preferablythe hats are lei'tunthe second dipping. inthe and adverse weather conditions. Other suitable waterproofing agents of the well known class of waterproofing agents used on cotton or other cellulosic material may be used for this purpose.

. Methacrylate resin is a good waterproofing agent;

and is incorporated in the abovelacquer-formula not only because of its uniform reflection proper ties but also because it functions as a water-.

proofing agent.

- Paooucr The process of the present invention produces properties oiundyed material, and having substantially complete and uniform penetration of the dye. The product possesses substantially the same shade'upon both the bruished and-um bruised portions of the fiber. Light is reflected substantially uniformlyfrom the entire product because the lacquer coating covers up the differences in. reflection which would otherwise be produced by the bruised andunbruised fibers. The palm fibers are resistant to water by reason of being coated with a lacquer containing a waterproofing agent;

Dyed palm fiber contains the reaction product of the dyes used in the dyeing process. 'Because the reaction product cannot be named with. periect accuracy, it is sometimes. hereinafter designated astne dyestuff. The product of the present invention is palm fibei containing at least one of each of class'A dyestufis and class B dyestuffs.

Panama hats made in accordance with the process of the present invention meet all of the commercial requirements of freedom from fading,

weather resistance, strength, etc.

Parts of the present invention may be used without others. Many modifications of" the process and product are possible without departing from thespirit of the present invention as described in this specification.

, What is claimed as-new is:

' 1. The process of dyeing slightly bruised sulfur-free Panama hats comprising the steps of I preparing a dyeing solution. containing water, an emulsifying agent, at least one dyestuff chosen aaeaeee fur-free. bleached Fanaina hats steps of: preparing a dyeing solution c water, an emulsifying agent. at least stufi chosen from the class consisting o dyestufis, and oil or spirit soluble dyestuiis, and at least one dyestufi chosen from the class consisting of direct dyestuffs, and neutral dyeing acid dyestuffs; penetratingly wetting out the Panama hats in water at a temperature of approximately 60" F. for about twelve hours; placing the wetted hats in the dyeing solution at a temperature'of approximately l l*".; raising the temperature of the dyeing soluticn' to about the boiling point within about twenty-five minutes; maintaining the dyeing solution at the boiling point for about an hour; and then withdrawing the'hats from the dyeing solution.

The process oi dyeing slightly cruised sul fur-free, untriinmed, bleached Panama hat bodies comprising the steps or": preparing adyew ing solutioncontaining water, an emulsifying agent, at least one dyestufi chosen from the class consisting of acetate dyestuffs, and oil or spirit soluble dyestuffs, and at least one dyestufi chosen from the class consisting of direct dyestuffs, and

neutral dyeing acid dyestufis; penetratingly wetting out the hat bodies'in a .l per cent solution of a powerful wetting agent at F. for five I .from the dyeing solution.

paring a dyeing solution containing water; an

emulsifying agent, at least one dyestuff chosen from the class consisting of acetate dyestuffs,

and oil or spirit soluble dyestuffs, and at least one dyestuii chosen from the class consisting'of direct dyestufis, and neutral dyeing acid dyes'tufi's; penetratingly wetting out the Panama hats; placing the wetted hats in the dyeing solution at a temgradually perature of approximately F.; raising the temperature of the dyeing solution to about the boiling point; maintaining the dyeing solution at about the boiling point for about an hour; and withdrawing the palm fibersirom the dyeing solution. I

- 3. The process of dyeing slightly bruised sulface.

4 5. An article formed. from woven palm fibers dyed in substantially level shades with at least onedyestufi chosen from the class consisting of acetate dyestufis, and oil or spirit soluble dyestuffs, and at least one dyestulf chosen from the class consisting of direct dyestuffs and neutral dyeing acid dyestufis.

I 6. An article as defined in claim 5 having a coating of lacquer thereover to provide the dyed palm fibers with a uniform lightreflecting sursoluble dyestuffs, and atleast one dyestufi chosen from the class consisting of direct dyestuffs and neutral dyeing acid dyestufis.

GEORGE M. menus. WILLIAM L. BRAUN. STANLEY o. HOFFMAN. 

